Formulations of random polymers for improving crude petroleum flow

ABSTRACT

The present invention is related to the use of formulations of new random copolymers and terpolymers, synthesized by a method of semi continuous emulsion polymerization, and that function as flow improvers, lowering the pour point and reducing the viscosity of Mexicans crude oils, which have gravities within the range of 9 to 30° API.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit under 35 U.S.C. §119 of MexicanPatent Application No. MX/a/2009/010135, filed Sep. 22, 2009, which ishereby incorporated by reference in its entirety.

FIELD OF INVENTION

This invention is related to the synthesis of random polymers, theirformulation and application as flow improvers of crude petroleum withAPI densities between 9 and 30° API. These flow improvers decreasepetroleum pour point and viscosity.

The random polymers considered in this invention were synthesized bysemi continuous emulsion polymerization causing the reaction of two orthree commercial monomers and were added as a formulation in Mexicancrude oils at concentrations between 250 and 4,000 parts per million.

BACKGROUND OF THE INVENTION

Crude oil and any of their distillates, such as diesel, gasoil, naphthaand kerosene, contain different percentages of paraffins, whichprecipitate when the temperature decreases and crystallize very oftencoating the hydrocarbon.

The crystallization and agglomeration of paraffins degrade the flowproperties of the oil or their distillates and break off the extractionprocedure, processing, transport, storage and the use of thehydrocarbon.

This paraffin agglomeration is often observed during winter, when theenvironmental temperature falls and approaches to the pour point,producing the obstruction and even the complete plugging of pipelines inrefineries, storage centers and other installations for petroleumprocessing.

Paraffin agglomeration takes place also in some crude distillates, inexample diesel, producing obstructions in the filters of internalcombustion motors, plugging heating pipes, which results in a badoperation.

When there is a cooling, paraffins disaggregate and form small crystalswhich interact forming a tridimensional network able to trap the liquidand increasing the viscosity. If this one happens in distillates likediesel, filter and valve stoppages are observed, but, when thisphenomenon occurs in crude oil, the petroleum suffers gelling anddeposits are formed on pipelines and storage tanks, provoking greatdamages to the production and storage capacity.

There are two kinds of flow improvers: nucleation and Crystal growingmodifiers (Odriozola et al, 2008). The first promote the formation oftiny paraffin crystals, whereas the second kind facilitates theappearance of great crystal groups. In both cases the formation of atridimensional crystal network is hindered. Nucleation modifiers areapplied in gas and diesel transport and processing because paraffincrystals are so tiny that they can traverse trough filters. In contrast,growing modifiers are specially employed in crude oils (Tomassen H P Met al, 1998).

Most common flow modifiers are polymers, some of them homopolymers andthe most copolymers. Homopolymers are obtained by reacting a singlemonomer while copolymers are synthesized from a combination of twodifferent copolymers (M1 and M2). Monomers forming a copolymer chain maybe arranged following an alternate sequence (alternate copolymerM₁M₂M₁M₂M₁M₂), or a succession of first monomers followed by asuccession of the second monomer (block copolymers M₁ M₁ M₁ M₁ M₂ M₂ M₂M₂) or a random sequence of monomers (M₁ M₂ M₁ M₁ M₂ M₂ M₂ M₁). Thislast kind of copolymers is specially characterized by their highhomogeneous composition. The monomer sequence arrangement in copolymerchains, just that composition homogeneity, has a strong influence ontheir application properties. The use of single terpolymers as petroleumflow improvers has not yet been reported.

In the specific case of polymers employed as petroleum flow improvers,branched polyolefins, alphaolefin and esters of unsaturated carboxylicacids copolymers, ethylene and vinyl esters of fat acid copolymers,vinyl acetate and alpha olefin copolymers, styrene maleic anhydridecopolymers, fatty acid amides and polyalkylacrylates, (Castro L V et al,2008).

More specifically, ethylene-vinyl acetate copolymers (EVA) are producedby BASF under the trade mark Keroflux (Eisenbeis A et al., 2005).

Some examples of petroleum flow improvers given by the internationalliterature are the following: European Patent No. EP0931825 B1 depicts aprocess for improving flow properties of oils with a sulfur contentlower than 500 ppm and a minimal paraffin content around 8% by weight,using mixtures of copolymers and terpolymers, at a rate of 15% to 50% byweight of copolymers consisting of: polyethylene from 87% to 92% mol;polyvinyl acetate from 6.5% to 12% mol and 4-methyl-polypentene from0.5% to 6% mol and terpolymers made of ethylene, vinyl esters and vinylacrylates, at a composition between 50 and 85% (Krull M et al, 2003).

U.S. Pat. No. 4,362,533 describes the synthesis and use of terpolymersas pour point depressors for crude oil middle distillates, made ofpolyethylene (45-75% wt.), at least 5% by weight of polyvinyl acetateand 5% by weight of polystyrene. These polymers present a homogeneousdistribution and composition of each monomer (Kidd, N. A., 1982).

European Patent No. 0136698A2 describes as a new flow improver a polymerwith content between 50 and 90% by weight of ethylene, 10 to 40% byweight of esters of polyvinyl, 0.2 to 10% by weight of olefins and 2% to25% by weight of aromatic vinyl, its molecular mass vary from 1,000 to50,000, more preferably 2,000 to 10,000 Dalton. The polymer is added atconcentrations between 0.03 and 0.10% by weight, being very effective todecrease the pour point of oils and middle distillates of petroleum(Chen J C S, 1985).

U.S. Patent Publication No. 2004/0092665 describes the use of copolymersconstituted by a butylic fraction (isoprene, butadiene,2,4-dimethyl-butadiene, 2,4-hexadiene and halogenated derivatives, amongothers) and styrenic fraction (alpha-methyl-styrene and styrene) (PazurR et al, 2004).

Copolymer synthesized from vinyl esters, alkyl acrylate and styrene wereadded (200 to 4,000 ppm) into Mexican crude oils and diminishedviscosity and pour point (Castro L V et al, 2008). These additives weresynthesized by semi continuous emulsion polymerization and, afterwards,characterized by spectroscopic and calorimetric techniques, in order toensure a random distribution in the chains and a homogeneouscomposition. The synthesis procedure showed their efficiency to avoidthe formation of homopolymer mixtures. The performance of these productsdepends strongly on this molecular feature and on the absence of longsequences of a single monomer.

In Mexico, the reserves of light crude oil diminishes very fast and, inconsequence, only heavy and extra-heavy crude oils will be processed inthe future by the national system of refineries. This situationrepresents a challenge because of the technical and economicaldifficulties related to this problem. Therefore, it is very important tofind a solution to the problem of the low API gravity and high viscosityof the Mexican crude oils (Camacho-Bragado et al, 2002).

Taking in account the great importance of these technical and economicalrequirements, a series of formulations of new random copolymers andterpolymers dissolved in different solvents was prepared. All thesepolymers were prepared by emulsion polymerization and showed aconsiderable performance as pour point and viscosity decrease agents insome Mexican crude oils. It is important to remark that none of thereferences mentioned above neither disclose nor claim the application ofpolymers and/or formulations whose main characteristic is that polymersare composed of combinations of two or three acrylic, vinylic andstyrenic monomers together at random which main component are styrenictype.

BIBLIOGRAPHIC REFERENCES

-   Ahlers W. et al. U.S. Patent Publication No. 2007/0094920 (2007).-   Bharambe Dinakar P. and Soni Hemant P. Synthesis and Evaluation of    Polymeric Additives as Flow Improvers for Indian Crude Oil. Iranian    Polymer Journal 15 943-954 (2006).-   Borthakur A., Chanda D., Dutta Choudhury S. R., Alkyl fumarate-vinyl    acetate copolymer as flow improver for high wxy Indian crude oils.    Energy & Fuels 10 844-848 (1996).-   Camacho-Bragado G. A., Santiago P, Marin-Almazo M, Espinoza M,    Romero E. T., Murgich J, Rodríguez-Lugo V, Lozada-Cassou M and    Jose-Yacaman M, Fullerenic structures derived from oil asphaltenes.    Carbon 40 2761-2766 (2002).-   Castro L V and Vazquez F. Copolymers as flow improvers for Mexican    crude oils. Energy and Fuel. 22 4006-4011 (2008).-   Castro Laura V. and Vazquez Flavio, Fractionation and    characterization of Mexican Crude oils. Energy and Fuels. 23    1603-1609 (2009).-   Charles Adams, Emulsion Polymerization process and reactor for such    a process. U.S. Pat. No. 6,569,961 B1. (2003).-   Chen J C S. Cold flow improver. EP0136698 (1985).-   Eisenbeis A, Ahlers W, Troetsch-Schaller I, Fechtenkoetter A and    Maehling F O. Fuel oil compositions with improved cold flow    properties. CA 2 548 008 A1 (2005).-   Jimenez-Angeles F, Duda Y, Odriozola G, and Lozada-Cassou M.    Population inversion of a NAHS Mixture Absorbed into a cylindrical    pore. J. Phys. Chem. C. 112 18028-18033 (2008).-   Kidd, N. A. Terpolymer of ethylene, vinyl acetate, and styrene as    pour point depressants for distillate fuel U.S. Pat. No. 4,362,533    (1982).-   Krull M and Reimann W. Process and product to improve cold flow    properties of fuel oils. EP 0931825 B1 (2003).-   Nuñez S. Ma. Del Carmen. Introducción a la reología, D. R. Instituto    Politécnico Nacional, 2001.-   Odriozola G, Jimenez-Angeles F and Lozada-Cassou M, Entropy driven    key-lock assembly. J. Chem. Phys. 129 101-111 (2008).-   Pazur R and Sumner A J. Butyl polymer composition having improved    cold flow properties U.S. Patent Publication No. 2004/0092665    (2004).-   Reyes-Mercado Y., Vazquez F., Rodriguez-Gomez F. J., Duda Y. Effect    of the acrylic acid content on the permeability and water uptake of    poly(styrene-co-butyl acrylate) latex films. Colloid Polym Sci. 286    603-609 (2008).-   Ronningsen Hans Petter and BjØrndal. Wax precipitation from North    Sea crude oils: 1. Crystallization and dissolution temperatures, and    Newtonian and non-newtonian flow properties. Energy & Fuels 5    895-908 (1991).-   Tomassen H P M, Van de K C C, Reynhout M J and Lin J. Polymeric flow    improver additives U.S. Pat. No. 5,721,201 (1998).-   Torres E, Dutta N, Roy C. N. and Matisons J. Effect of composition    on the solution rheology of Stearyl Methacrylate-co-styrene-co-vinyl    pyrrolidinone in paraffinic base oil. Polymer Engin. Sci. 44 736-748    (2004).

BRIEF DESCRIPTION OF THE DRAWINGS

The following figures are given in order to understand clearly theperformance of the formulation of random polymers for improving crudepetroleum flow and are used as reference of the application examples.

FIG. 1 shows the effect of the pour point decrease activity in lightcrude oil of examples E1-E4, evaluated between 200 and 4,000 ppm, andcompared to the commercial product COM-01.

FIG. 2 shows the effect of the pour point decrease activity in middlecrude oils, evaluated from 250 to 4,000 ppm.

FIG. 3 exhibits the effect of the reducing viscosity activity at 20° C.in heavy crude oil in examples 6, 7, 8, 9 and 10, evaluated at 1,000ppm.

FIG. 4 presents the effect of the viscosity decrease activity at 20° C.in heavy crude oil of examples 11, 14 and 16 evaluated at 1,000 ppm.

FIG. 5 exposes the effect of the viscosity decrease activity in heavycrude oil at different temperatures of examples 11, 12 and 16 evaluatedat 500 and 1,000 ppm.

FIG. 6 shows the effect of the decrease activity of the activity inheavy crude oil at different temperatures of examples 12, COM-01 andCOM-02, evaluated at 1,000 ppm.

DETAILED DESCRIPTION OF THE INVENTION

The present invention consists of the synthesis of new random copolymersand terpolymers by semicontinuous emulsion polymerization and thepreparation of formulations (random copolymers and terpolymers combinedwith organic solvents) and their application as flow improvers andviscosity reducers. The invention is also directed to a process ofreducing the viscosity and depressing the pour point of crude oil bymixing the crude oil with an effective amount of the random copolymersand terpolymers to reduce the viscosity and depress the pour point. Inschemes 1 to 3 the copolymer structure (random combination of a coupleof monomers) are shown and in scheme 4 the terpolymer structure obtainedfrom three monomers combination are shown:

Copolymers

Terpolymers

where:

-   R₁, R₂, R₃ and R₄ are represented by independent radical groups    listed below:-   R₁=C₆H₅, CH₃C₆H₄, (CH₃)₂C₆H₃, (CH₃)₃C₆H₂, (CH₃)₃CC₆H₄;-   R₂=H, CH₃;-   R₃=CH₃, C₂H₅, C₄H₉, C₆H₁₃, C₈H₁₇, C₁₀H₂₁, C₁₂H₂₅, C₁₈H₃₇;-   R₄=H, CN.    and where:-   x, y, z, m, n, p, q, u and v are numbers within the following    ranges:-   x=from 2 to 900, preferably from 20 to 850, even more preferably    from 25 to 700;-   z=from 1 to 300, preferably from 10 to 235, still more preferably    from 20 to 220;-   y=from 1 to 226, preferably from 10 to 210, still more preferably    from 20 to 200;-   m=from 10 to 700, preferably from 20 to 650, still more preferably    from 40 to 620;-   n=from 1 to 220, preferably from 10 to 200, still more preferably    from 20 to 170;-   p=from 1 to 700, preferably from 25 to 650, still more preferably    from 60 to 620;-   q=from 1 to 50, preferably from 5 to 45, even more preferably from    10 to 40;-   u=from 1 to 220, preferably from 10 to 200, more preferably from 30    to 170;-   v=from 1 to 50, preferably from 10 to 40, more preferably from 15 to    30.

Additionally, the molecular weights are in the following ranges, from1,000 to 100,000 Daltons, preferably between 5,000 and 90,000 Daltonsfor the case of copolymers and from 1,000 to 140,000, preferably from2,000 to 100,000 Daltons in the case of random terpolymers.

The copolymers and terpolymers of the present invention are prepared byemulsion polymerization technique, which presents ecological advantageswhen using water as dispersion medium avoiding the use of large amountsof organic solvents during the synthesis stage. Emulsion polymerizationis widely used for the synthesis of adhesives, paints and varnishes, buthas not reported used as improvers in crudes oil (Charles Ad 2003).

The following describes by way of example, it does not imply anylimitation, the monomers used in the synthesis of polymers object ofthis invention: methyl acrylate, tert-butyl methacrylate, butylacrylate, butyl methacrylate, hexyl acrylate, hexyl methacrylate,iso-butyl acrylate, iso-butyl methacrylate, ethyl acrylate, ethylmethacrylate, tert-butyl acrylate, 3,5,5-trimethyl-hexyl acrylate,iso-decyl acrylate, iso-decyl methacrylate, iso-octyl acrylate, laurylacrylate, lauryl methacrylate, octadecyl acrylate, 2-ethyl-hexylacrylate, 2-ethyl-hexyl methacrylate, styrene, 2,4,6-trimethyl-styrene,2,4-dimethyl-styrene, 3-methyl-styrene, 4-methyl-styrene,2-methyl-styrene, 4-tert-butyl-styrene, α,2-dimethyl-styrene,α-methyl-styrene, methyl styrene, vinyl acetate, and cyanovinyl acetate.

The synthesis of polymers (random copolymers and terpolymers) of thepresent invention, which are effective in the lowering of the pour pointand viscosity reduction of light, median and mainly heavy crudes oil,comprising seven stages:

-   1) Preparation of the initiator.-   2) Preparation of surfactant solutions ((Anionic(A) and/or nonionic    (B))-   3) Preparation of buffer solution-   4) Preparation of the monomers (combination of two monomers for    copolymers and three monomers for terpolymers)-   5) Preparation of Cuba or foot main reactor.-   6) Preparation tank addition.-   7) Polymerization of combinations of two or three monomers.

The synthesis of polymers using the semicontinuous method was used(Reyes-Mercado Y. et al.) which is described below. This method isillustrative but not limiting:

-   1) Initiator preparation: In a balloon flask equipped with magnetic    stirring, is placed a suitable amount of initiator, and dissolved in    deionized water and kept stirring for 10 minutes. These amounts can    vary between 0.5 and 15.0 g of initiator per 100.0 g of deionized    water. As initiators, potassium, sodium or ammonium persulfates, as    well as sodium or potassium methabisulfite and benzoyl hydroperoxide    can be used.-   2) Preparation of surfactant solutions. In a flask equipped with    magnetic stirring, are placed an appropriate amount of surfactant A    (ionic) and surfactant B (nonionic), both are dissolved in deionized    water and kept stirring for 40 minutes. These amounts can vary    between 0.5 and 50.0 g of surfactant per 100.0 g of deionized water.-   3) Preparation of buffer solution. The buffer ensures no abrupt    changes in the pH of the system. In a balloon flask equipped with    magnetic stirring ball, is placed an appropriate amount of buffer,    (for example sodium or potassium bicarbonate) dissolved in deionized    water and kept stirring for 10 minutes. These amounts can vary    between 0.5 and 15.0 g of initiator per 100.0 g of deionized water.-   4) Preparation of the monomers. In a volumetric flask, is placed the    appropriate amount of monomer or monomers required (two monomers for    copolymers and three monomers for terpolymers). The compositions of    each monomer in the mixture can vary between 1% and 99%, preferably    between 5% and 90% compared to total monomer. It requires a transfer    agent (for example dodecyl or terdodecyl mercaptane) to control the    molecular weights of polymers. The transfer agent is added to the    mixture of monomers. The amount of transfer agent can vary between    0.0 and 12.0 g per 100.0 g of monomer, according to the desired    molecular weight. This mixture is stirred for about 5 minutes.-   5) Preparation of cuba or foot main reactor: The reactions were    conducted in a glass reactor of one liter capacity with a heating    jacket through which water is recirculated at constant temperature.    Agitation is achieved by a propeller of two sheets of Teflon-coated    material, moved by a mechanical stirrer of varying acceleration. The    reactor also has a condensation system, with connections for    temperature monitoring, connection for inert gas injection and    sampling connection. The reactor is filled with a solution of    appropriate amounts of surfactant A and surfactant B, buffer    solution, deionized water and a small amount of mixture of monomers.    These amounts can vary between 1.0 and 25.0 g of solution per 100.0    g of monomers. Deionized water is added, which can vary between 70    and 300 g. Subsequently, the reactor is pressurized with nitrogen to    ensure inert atmosphere. The temperature was set between 50 and    90° C. to ensure the smooth progress of polymerization. After 10 to    40 minutes of stirring, is added the appropriate amount of initiator    solution. This amount can vary between 1.0 and 20.0 g of initiator    solution. Again, the reactor is pressurized with nitrogen to ensure    polymerization.-   6) Preparation tank addition. The addition tank was carried out in a    glass flask of one liter capacity with connection to suction of    dosing pump and with controlled magnetic stirring. Once the    preparation of the foot of cuba proceed to slowly add the remaining    monomer mixture, solutions of surfactant A, B and the remaining    buffer in addition to the tank. Finally, deionized water is added,    which can vary between 70.0 and 300.0 g per 100.0 g of monomers.-   7) Copolymerization or terpolymerization of monomers. It connects    the addition tank to the main reactor (foot of cuba), through a    metering pump. The ratio of feed addition tank ranges from 0.003 to    0.009 g/mL-min, more preferably 0.004 to 0.007 g/mL-min. This rate    of addition guarantees the existence of monomer deficiency in the    main reactor and ensures that the pairs or trios of monomers react    with each other and respectively forming random copolymers or    terpolymers. Do not place the addition in the range of speeds of    addition, as this will form large sequences of a single monomer    within the chains and even form mixtures of homopolymers.

To obtain the desired molecular weight after the addition of themonomers, it is necessary to complete the reaction by adding smallamounts of initiator and increasing the temperature to 90 and 95° C. forone hour. The copolymer or terpolymer was subsequently placed in sealedcontainers. Random copolymer or terpolymer reactions achieve conversionsbetween 98.00-99.99% by weight (Castro L V et al, 2008). The productsobtained have latex form. The dispersion of latex in water is easier toprocess and avoids the use of organic solvents, without health and theenvironment risks. Stressing further that without this synthesisprocedure, it is virtually impossible to obtain the random polymers(copolymers and terpolymers).

Once obtained copolymers and terpolymers were characterized using theinstrumental methods:

-   1.—Infrared brand model Thermo Nicolet® AVATAR 330 Spectrometer    Fourier Transform using the method of film technique with software    version 7.0 OMNIC®.-   2.—Nuclear Magnetic Resonance Jeol Eclipse equipment, operating at    300 MHz and 75 MHz for ¹H and ¹³C spectra respectively, using    deuterated chloroform as solvent; the shifts are indicated in parts    per million, about tetramethylsilane (TMS) signal, as internal    standard.-   3.—Size exclusion chromatograph Agilent® model 1100 (CET), with    PLgel column and using tetrahydrofuran (THF) as eluent, to calculate    the molecular distribution of copolymers and terpolymers and the    polydispersity index (I).

Molecular masses, polydispersity indices and spectroscopiccharacteristics are now described in Tables 1 and 2, which does not meanlimitation:

TABLE 1 Copolymers number molecular masses (Mn) and polydispersity index(I) measured by (CET). Polydispersity Copolymers Mn (g/mol) Index IPhysical State E-1 2938 1.4 Viscous semi solid E-2 2213 1.2 Viscous semisolid E-3 9279 2.1 Viscous semi solid E-4 1691 1.5 Viscous semi solidE-5 55278 2.8 Viscous semi solid

TABLE 2 Terpolymers number molecular masses (Mn) and polydispersityindex (I) measured by (CET). Polydispersity Terpolymers Mn (g/mol) IndexI Physical state E-6 1448 1.9 Viscous semi solid E-7 1109 3.3 Viscoussemi solid E-8 139900 2.3 Viscous semi solid E-9 2057 1.8 Viscous semisolid E-10 23488 1.7 Viscous semi solid E-11 2223 3.3 Viscous semi solidE-12 21547 2.1 Viscous semi solid E-13 2954 1.7 Viscous semi solid E-1420701 1.9 Viscous semi solid E-15 1184 2.0 Viscous semi solid E-16 68162.7 Viscous semi solid

EXAMPLES

The following examples are presented to illustrate the best mode ofrandom polymer synthesis, formulation and implementation as flowimprovers in crudes oil with API gravities ranging from 9 to 30. Theseexamples should not be regarded as limiting what is claimed.

E-1

Poly(styrene)_(p)-poly(acrylate)_(q) (R₁=phenyl, R₂=Hydrogen, R₃=butylacrylate), with the following composition 30 g of monomer A and 70 g ofmonomer B, with 8% of transfer agent: viscous semisolid; I.R. ν cm⁻¹:3082.7, 3060.3, 3026.5, 2926.3, 2854.5, 1943.5, 1870.6, 1801.7, 1729.9,1601.6, 1493.4, 1452.6, 1355.4, 1252.3, 1160, 1068.2, 1029.08, 944.4,841.3, 759.6, 699.6, 543.8; ¹³C RMN (CDCl₃): 170.5, 145.4, 128.1, 127.8,125.8, 70.6, 40.5, 32.0, 29.7, 28.9, 22.8, 21.0, 14.2.

E-2

Poly(acetate)_(u)-poly(acrylate)_(v) (R₂=Hydrogen, R₃=butyl acrylate,R₄=Hydrogen), with the following composition 30 g of monomer A and 70 gof monomer B, with 8% of transfer agent: viscous semisolid; I.R. ν cm⁻¹:2959.4, 2931.7, 2873.6, 1736.6, 1459.9, 1371.7, 1237.7, 1167.6, 1119.1,1023.5, 942.9; ¹³C RMN (CDCl₃): 174.7, 170.3, 70.5, 69.9, 64.6, 62.2,41.5, 40.4, 39.5, 31.9, 39.65, 29.7, 29.4, 28.9, 22.7, 20.9, 19.2, 14.1,13.8.

E-3

Poly(styrene)_(m)-poly(acetate)_(n) (R₁=phenyl, R₂=Hydrogen,R₄=Hydrogen), with the following composition 30 g of monomer A and 70 gof monomer B, with 2% of transfer agent: viscous semisolid; I.R. ν cm⁻¹:3445.7, 3081.8, 3059.5, 3025.5, 2923.6, 2851.5, 1943.8, 1870.5, 1803.3,1736.2, 1601.1, 1492.8, 1452.0, 1372.2, 1244.8, 1118.5, 1028.2, 757.4,698.6, 540.2; ¹³C RMN (CDCl₃): 145.3, 128.0, 125.7, 70.6, 44.0, 40.6.

E-4

Poly(styrene)_(m)-poly(acetate)_(n) (R₁=phenyl, R₂=Hydrogen,R₄=Hydrogen), with the following composition 30 g of monomer A and 70 gof monomer B, with 8% of transfer agent: viscous semisolid; I.R. ν cm⁻¹:3059.7, 3025.5, 2923.8, 2852.3, 1943.4, 1871.6, 1738.2, 1601.1, 1492.8,1452.1, 1372.8, 1243.1, 1108.7, 1027.9, 757.2, 698.9, 540.3; ¹³C RMN(CDCl₃): 170.5, 145.4, 128.1, 127.8, 125.6, 70.6, 40.6, 31.9, 29.6,22.8, 21.0, 14.2.

E-5

Poly(styrene)_(m)-poly(acetate)_(n) (R₁=phenyl, R₂=Hydrogen,R₄=Hydrogen), with the following composition 70 g of monomer A and 30 gof monomer B, with 0% of transfer agent: Solid; I.R. ν cm⁻¹: 3453.6,3025.4, 2922.8, 1943.9, 1870.8, 1732.2, 1601.4, 1493.3, 1452.7, 1373.4,1242.9, 1119.8, 1025.9, 946.2, 757.6, 698.5, 539.4; ¹³C RMN (CDCl₃):170.4, 145.4, 128.0, 125.7, 70.6, 69.7, 67.1, 40.6, 39.3, 21.1.

E-6

Poly(styrene)_(x)-poly(acetate)_(y)-poly(acrylate)_(z) (R₁=phenyl,R₂=Hydrogen, R₃=C₄H₉, R₄=Hydrogen), with the following composition 30 gof monomer A, 20 g of monomer B and 50 g of monomer C, with 8% oftransfer agent: viscous semisolid; I.R. ν cm⁻¹: 2958.1, 2929.9, 2872.9,1731.2, 1453.5, 1372.3, 1238.8, 1163.3, 1066.6, 1028.6, 700.8; ¹³C RMN(CDCl₃): 175.3, 128.4, 127.8, 126.4, 70.5, 69.8, 64.3, 41.7, 41.2, 39.5,31.9, 30.7, 29.7, 29.4, 28.9, 22.7, 21.0, 19.2, 13.8.

E-7

Poly(styrene)_(x)-poly(acetate)_(y)-poly(acrylate)_(z) (R₁=phenyl,R₂=Hydrogen, R₃=tert-butyl, R₄=hydrogen): with the following composition30 g of monomer A, 50 g of monomer B and 20 g of monomer C, with 8% oftransfer agent: viscous semisolid; I.R. ν cm⁻¹: 3026.4, 2926.3, 1731.6,1493.4, 1372.0, 1452.6, 1242.1, 1161.0, 1028.4, 759.7, 699.8; ¹³C RMN(CDCl₃): 175.9, 170.5, 145.2, 143.8, 128.3, 113.9, 70.5, 63.8, 43.1,1.2, 39.2, 33.8, 32.0, 29.7, 22.8, 21.1, 19.2, 14.2, 13.8.

E-8

Poly(styrene)_(x)-poly(acetate)_(y)-poly(acrylate)_(z) (R₁=C₆H₄CH₃,R₂=hydrogen, R₄=hydrogen, R₅=C₄H₉): with the following composition 30 gof monomer A, 50 g of monomer B and 20 g of monomer C, with 0% oftransfer; viscous semisolid; I.R. ν cm⁻¹: 3438.5, 3059.9, 3026.9,2925.8, 1945.8, 1873.8, 1803.1, 1729.5, 1602.1, 1492.5, 1451.1,1356.4,1249.7, 1156.9, 944.6, 840.9, 758.5, 700, 541.6; ¹³C RMN (CDCl₃):175.8, 170.5, 145.3, 128.1, 127.7, 125.9, 70.6, 63.8, 41.8, 30.6, 21.0,19.1, 13.8.

E-9

Poly(styrene)_(x)-poly(acetate)_(y)-poly(acrylate)_(z) (R₁=C₆H₄CH₃,R₂=hydrogen, R₃=C₄H₉, R₄=hydrogen): with the following composition 20 gof monomer A, 50 g of monomer B and 30 g of monomer C, with 8% oftransfer agent; viscous semisolid; I.R. ν cm⁻¹: 3442.0, 3082.9, 3026.7,2928.6, 1944.4, 1870.9, 1731.5 16017, 1493.7, 1453.0, 1373.0, 1242.0,1160.7, 1028.0, 943.9, 841.3, 759.9, 841.3, 759.9, 699.0, 544.7; ¹³C RMN(CDCl₃): 175.2, 128.4, 64.2, 41.3, 34.8, 31.9, 30.7, 29.7, 28.9, 22.7,21.1, 19.2, 13.8.

E-10

Poly(styrene)_(x)-poly(acetate)_(y)-poly(acrylate)_(z) (R₁=C₆H₅,R₂=hydrogen, R₃=C₆H₁₃, R₄=hydrogen), with the following composition 20 gof monomer A, 50 g of monomer B and 30 g of monomer C, with 1% oftransfer agent; viscous semisolid; I.R. ν cm⁻¹: 3437.9, 3026.5, 2926.6,1944.7, 1873.3, 1728.5, 1601.6, 1493.0, 1451.5, 1354.8, 1250.3, 1155.4,1028.3, 759.3, 699.3; ¹³C RMN (CDCl₃): 176.0, 170.6, 144.3, 128.3,125.9, 70.5, 63.9, 41.2, 31.9, 29.7, 28.9, 22.8, 21.1.

E-11

Poly(styrene)_(x)-poly(acetate)_(y)-poly(acrylate)_(z) (R₁=C₆H₄CH₃,R₂=hydrogen, R₃=C₂H₅, R₄=hydrogen), with the following composition 20 gof monomer A, 70 g of monomer B and 10 g of monomer C, with 8% oftransfer agent; viscous semisolid; I.R. ν cm⁻¹: 3059.9, 3025.9, 2924.8,2852.9, 1943.4, 1871.3, 1802.9, 1730.9, 1493.0, 1452.3, 1243.9, 1154.9,1028.6, 758.0, 699.2, 541.1; ¹³C RMN (CDCl₃): 175.9, 170.4, 145.3,128.2, 125.8, 70.6, 63.8, 46.3, 40.6, 32.0, 30.5, 29.7, 29.4, 22.8,13.8.

E-12

Poly(styrene)_(x)-poly(acetate)_(y)-poly(acrylate)_(z) (R₁=C₆H₅,R₂=hydrogen, R₃=C₄H₉, R₄=hydrogen), with the following composition 20 gof monomer A, 70 g of monomer B and 10 g of monomer C, with 1% oftransfer agent; viscous semisolid; I.R. ν cm⁻¹: 3026.3, 2923.6, 1944.5,1873.0, 1803.8, 1730.3, 1601.6, 1492.2, 1449.6, 1371.2, 1243.4, 1152.7,1027.7,945.0, 908.5, 757.1, 700.3, 539.9; ¹³C RMN (CDCl₃): 145.3, 128.0,125.7, 70.6, 63.9, 44.3, 41.1, 40.5, 30.6, 19.1, 13.8.

E-13

Poly(styrene)_(x)-poly(acetate)_(y)-poly(acrylate)_(z) (R₁=C₆H₅,R₂=hydrogen, R₃=C₆H₁₃, R₄=hydrogen), with the following composition 20 gof monomer A, 10 g of monomer B and 70 g of monomer C, with 8% oftransfer agent; viscous semisolid; I.R. ν cm⁻¹: 3447.2, 2959.4, 2870.5,1730.9, 1604.2,1456.5, 1371.6, 1239, 1164.3, 1065.91026.3, 944.6, 840.4,759.7, 702.0; ¹³C RMN (CDCl₃): 175.2, 128.4, 64.2, 41.3, 34.8, 31.9,30.7, 29.7, 28.9, 22.7, 21.1, 19.2, 13.8.

E-14

Poly(styrene)_(x)-poly(acetate)_(y)-poly(acrylate)_(z) (R₁=C₆H₄CH₃,R₂=hydrogen, R₃=C₄H₉, R₄=hydrogen), with the following composition 20 gof monomer A, 10 g of monomer B and 70 g of monomer C, with 1% oftransfer agent; viscous semisolid; I.R. ν cm⁻¹: 3446.2, 2959.0, 2873.5,1732.2, 1453.0, 1372.9, 1239.5, 1163.8, 1117.9, 1066.3, 1024.2, 943.9,701.6; ¹³C RMN (CDCl₃): 175.0, 170.2, 0.5, 64.6, 41.4, 39.1, 35.3, 30.7,20.9, 19.2, 13.8.

E-15

Poly(styrene)_(x)-poly(acetate)_(y)-poly(acrylate)_(z) (R₁=C₆H₅,R₂=hydrogen, R₃=C₆H₁₃, R₄=hydrogen), with the following composition 60 gof monomer A, 30 g of monomer B and 10 g of monomer C, with 8% oftransfer agent; viscous semisolid; I.R. ν cm⁻¹: 3026.6, 2925.9, 2854.3,1732.9, 1601.6, 1492.8, 1451.4, 1372.2, 1241.3, 1156.9, 1026.6, 945.7,758.2, 700.5; ¹³C RMN (CDCl₃): 170.5, 128.3, 70.5, 41.2, 39.3, 31.9,29.4, 22.8, 14.2, 13.8.

E-16

Poly(styrene)_(x)-poly(acetate)_(y)-poly(acrylate)_(z) (R₁=C₆H₅,R₂=hydrogen, R₃=C₄H₉, R₄=hydrogen), with the following composition 60 gof monomer A, 30 g of monomer B and 10 g of monomer C, with 1% oftransfer agent; viscous semisolid; I.R. ν cm⁻¹: 3442.9, 3026.0, 2921.8,1944.4.

The random polymers (copolymers and terpolymers) of the presentinvention were formulated using various solvents and assessed as flowimprovers, either reducing the viscosity and/or reducing the pour pointin Mexican crude oils whose API gravity is between 9 to 30, thefollowing results are illustrative way do not mean any limitation.

Formulations of Copolymers and their Assessment as Pour Point ReducingAgents for Light and Medium Crude Oils

Different concentrated solutions of alternating copolymers of 1 to 60%by weight, preferably 5 to 40% by weight, were prepared using solventswhose boiling point falls within the range of 35 to 200° C., preferablyxylene, toluene, benzene, methyl ethyl ketone, kerosene, turbosine,naphtha, individually or in mixtures, so added small volumes ofdissolution and avoided the effect of the solvent influenced in theevaluation of the pour point. Alternating copolymers were evaluated inconcentrations in the range of 100 to 4,000 ppm.

Light crude oil used in the present invention was characterized as shownbelow in Table 3.

TABLE 3 Physicochemical and physical characterization of light, mediumand heavy crude oils (Castro L V et al, 2009). Parameter Light MediumHeavy API density 29.6 21.3 15.8 Salt content 23.0 kg/1,000 bls 1090kg/1,000 bls 1.1 kg/1,000 bls Wax content 3.02 3.83 4.27 (wt %) Water bydistil- 0.8 1.8 0.10 lation (vol %) Pour Point −21 −24 −2 (° C.) SARAAnalysis (wt %) Saturates 38.44 26.53 10.49 Aromatics 14.59 14.74 9.0Resins 41.44 47.60 64.12 Asphaltenes 5.53 11.13 16.39

The copolymers were evaluated simultaneously with commercial copolymerstype EVA (ethylene-vinyl acetate), as reducing agents of the pour pointand as a reference.

The assessment procedure is described below: the sealed bottles withinsert number and lid is indicated by the number of compounds to assessplus one that corresponds to the crude oil without additives; each ofthem was added with crude oil to the 80 mL mark. All the bottles wereplaced in a water bath at a controlled temperature in 60° C. for 30minutes, at the end of that time was added above the aliquot of thedissolution alternating copolymers and the commercial copolymersformulations; all the bottles shook for 4 minutes at a rate of 2 beatsper second and later placed for 20 minutes in ultrasonic bath withcontrolled temperature of 60° C. After agitation, the test pieces wereplaced according to the method ASTM D-97 and left at least 22 hours atroom temperature, the evaluation was the performed. All the copolymers,the reason of this invention, and commercial formulations were assessedat different concentrations in the range from 200 to 4,000 ppm. Asreference was also prepared a sample of crude oil only with the solvent(without polymer addition) and which is referred to as untreated.

As a demonstration, which does not involve limitation, results aredisplayed, in FIGS. 1 and 2, the evaluation of copolymers of examples1-4, for a concentration range of 200 and 4,000 ppm, crude light andmedium respectively; commercial formulations are follows:

-   COM-01: {copolymer of ethylene and 75/25, vinyl acetate MN=38678    Daltons (20%) with solvent (80%).}-   COM-02: {ethylene and vinyl 60/40 (p./p.), MN acetate    copolymers=52383 Daltons (20%) with solvent (80%).}

FIG. 1 presents the outcome of examples E1-E4 as pour point depressantsin light crude. Example 4 is the only one that reduces in greaterproportion the pour point, corresponding to the example that has lowermolecular weight number. The pour point is significantly reduced indosages for example 4 and COM-1 between 500 and 2,000 ppm regarding oilwithout adding with copolymers (untreated).

E1 and E2 examples do not have an effect as pour point depressants. Thiscan be explained by the lack of interaction between acrylates units ofcopolymers with components of crude oil, especially with waxes, whilestyrene-vinyl copolymers have better affinity with crude oil.

FIG. 2 presents the results of examples E1-E4 as pour point depressantsin medium crude oil. The example E4 showed the best performance to beevaluated in medium crude oil, which contains more aromatic componentsand more content of asphaltenes compared to the light crude oil.

The effect of molecular mass in examples 3 and 4 is present to compareresults in FIG. 2, this last being the most satisfactory.

The copolymer COM-1 presents some reduction at the pour point in mediumcrude oil, but not in the same way did it with light crude oil. Thisdifference in behavior can be attributed to the increase of asphaltenesin the medium crude oil (11.13% by weight), as well as the increase inmolecular mass of these.

Random Terpolymers Formulation and their Evaluation as ViscosityReducing Agents in Heavy Crude Oil.

Tests consisted in the realization of temperature sweeps to determinethe behavior of the viscosity of the heavy crude with added randompolymers, depending on temperature; all crude oil samples were subjectedto a constant shear rate of γ=50 sec⁻¹, in a temperature range of 20 to80° C.

Prepared different concentrated solutions of each of the randomterpolymers at 5 to 40% by weight, using solvents whose boiling pointfalls within the range of 35-200° C., preferably xylene, toluene,benzene, methyl ethyl ketone, kerosene, turbosine, naphtha, individuallyor in mixtures, so added small volumes of dissolution and found that theeffect of the solvent did not influence the assessment of viscosity.Random terpolymers were evaluated simultaneously with commercial typeEVA copolymers (vinyl, with 25% and 40% ethylene-acetate copolymersweight of vinyl acetate), as reducing agents of viscosity inconcentrations in the range of 250 to 4,000 ppm. The characterization ofheavy crude oil used in this evaluation is indicated in Table 3.

The assessment procedure described below: the sealed bottles with insertnumber and lid is indicated by the number of compounds to assess plusone that corresponds to the crude without additives; each of them addedcrude oil to the 80 mL mark. All the bottles were placed in a water bathat a controlled temperature in 40 ° C. for 15 minutes, at the end ofthat time was added above the aliquot of the dissolution of the randomterpolymers and the commercial copolymers formulations; all the bottlesshook during 4 minutes, 2 beats per second and later 20 minutes inultrasonic bath with controlled temperature of 60° C. After agitatedremained at rest at room temperature, then perform the evaluation. Allthe terpolymers reason for this invention and commercial formulationswere assessed at different concentrations in the ranger of 250 to 1,000ppm for a solution to 20% of polymer in any solvents or mixtures of themmentioned above although preferably used xylene or toluene. Crude oilsamples without polymer were used as untreated or reference.

An important parameter to reduce the viscosity of crude oil and improvefluidity is the manipulation of temperature. The temperature stronglyinfluences the viscosity of high molecular mass of crude oil components.Increasing temperature increases the level of clutter the structures ofthe components of crude oil, resulting in reduce the viscositydrastically (Borthakur a. et al, 1996).

Heavy oil samples were performed rotational testing at differenttemperatures which provide information about the flow materialproperties and its behavior respect to temperature.

For this part of the evaluation it was used a rheometer to study theinfluence of the terpolymers on the behavior of heavy oil withtemperature and rotational tests. The influence of polymers wasevaluated at concentrations preferably from 250 to 10,000 ppm (Nuñez S Met al 2001, Ronningsen H P et al 1991).

It was used a rheometer (Anton Parr) Physica MCR301 model. It wasperformed the measurement of viscosity at 20° C. using a cutting speedrange of 0.1 to 300 sec⁻¹, with these measurements was made graphicrepresentation of the coefficient of viscosity η depending on cuttingspeed γ, called viscosity curve η=f(γ), similarly the measurement wasmade of shear τ depending on cutting speed γ (Nuñez S M et al 2001,Bharambe D P et al 2006).

By way of demonstration, which does not imply any limitation, are shownin FIGS. 3, 4, 5 and 6, the results of the evaluation described above,dosing at 500 and 1,000 ppm of a 20% solution of polymer at atemperature of 20° C. (Torres E et al 2004, Ahlers W et al 2007):

FIG. 3 in the top, shows the evolution of the viscosity of heavy oilwithout an additive (white) versus the cutting speed. It is also clearthat all the tested terpolymers (E6-E10) reduced the oil viscosity alongthe selected shear rate range, from 0.1 to 300 s⁻¹, at a constanttemperature of 20° C.

The terpolymer which exhibits the best performance is theP(BuA-co-AV-co-S) 20/30/50 (E7), that has a low molecular weight ( M_(w)=3705 Daltons). Compositionally speaking is the one with greaterstyrene content, less composition of acetates and median acrylategroups.

In order to compare the terpolymers with the best viscosity reducingeffect, reference is made to FIG. 4, where evaluations of heavy crudeoil without an additive (white) and with terpolymers E12, E14 and E16additives are reported, all of them of high molecular weight. The orderof reduction of viscosity is E12>E16>E14. The above results clearlydemonstrate the magnitude of the molecular mass number ( M _(w)) thatmust have the terpolymer. For a terpolymer is a good viscosity reducerit appears that must have a high composition of styrenic polymers,considerable composition of acrylate groups and low composition ofacetate groups.

FIG. 5 shows the viscosity curve of heavy crude with polymers E11, E12and E16, at temperatures from 20 to 32° C. and dosages of 1,000 ppm, andis observed that the sample of heavy oil with additive E12 presents aninitial reduction of 23.5%, and as the temperature increases to 30° C.,reduced viscosity is about 25.1%. In the same Figure, a way ofcomparison were included the results of percentage reduction of E16 andE11.

FIG. 6 shows the general behavior of heavy oil without an additive(untreated) and with different concentrations of polymer additives, andthat is where it can ratify the behavior of viscosity reduction withincreasing temperature on added oil. It is necessary to highlight thefact that at low temperatures (from 20 to 40° C.) the viscosity of heavyoil is reduced and at temperatures above 50° C. is noted that oil is nolonger sensitive to these polymers.

However, it is important to note that the main interest of thisinvention is focused on reducing the viscosity of heavy oil in thetemperature range of 20 to 30° C., since this range represents thenormal operating conditions at platforms and refineries.

The same Figure presents the results of the evaluation of two commercialcopolymers (COM-01 and COM-02) as viscosity reducers. Neither reducesthe viscosity of heavy crude. One of them has any influence even asviscosity reducer (COM-02). Even worse, the commercial copolymer(COM-01) increases the viscosity; in contrast, the random terpolymerE-12 significantly reduces the viscosity of heavy oil.

With the different sets of tests using synthesized terpolymer andcopolymers and added to different types of Mexican crude, it waspossible to identify both the effect that caused each of the monomersand the effective polymer molecular mass range ( M _(w)). Also, it waspossible to establish to the characterization tests should have beensubmitted crude oil, if it wanted to evaluate the pour point orviscosity reduction.

For Mexican crudes, commercial copolymer COM-01 is a good pour pointdepressant but not so good viscosity reducer. When there are significantamounts of asphaltenes in crude oils, the rheological behavior of thestructure of the copolymer COM-1 is considerably reduced (Castro M F etal, 2008). In contrast, E4 and E12 polymers proved to be good pour pointdepressants and viscosity reducers under conditions of processingvarious crudes oil used into platforms and refineries.

What is claimed is:
 1. A random polymer formulation, wherein the random copolymers have the following formula:

where: R₁, R₂ and R₄ are represented by independent radical groups listed below: R₁=C₆H₅, CH₃C₆H₄, (CH₃)₂C₆H₃, (CH₃) ₃C₆H₂, (CH₃)₃CC₆H₄; R₂=H, CH3; R₄=H, CN; m=from 10 to 700; n=from 1 to
 220. 2. A random polymer formulation according to claim 1, wherein m is from 20 to 650 and n is from 10 to
 200. 3. A random polymer formulation according to claim 2, wherein m is from 40 to 620 and n is from 20 to
 170. 4. A random polymer formulation according to claim 1, wherein said random polymer formulation comprises a mixture of copolymers having molecular weights in number ranging between 2,000 to 90,000 Daltons.
 5. A random polymer formulation according to claim 4, wherein said molecular weights range in number between 5,000 and 80,000 Daltons.
 6. A random polymer formulation, wherein said random polymer formulation comprises random copolymers having the formula:

where: R₂, R₃ and R₄ are represented by independent radical groups listed below: R₂=H, CH₃; R₃=CH₃, C₂H₅, C₄H₉, C₆H₁₃, C₈H₁₇, C₁₀H₂₁, C_(l2)H₂₅, C₁₈H₃₇; R₄=H, CN; u=from 1 to 220; v=from 1 to
 50. 7. A random polymer formulation according to claim 6, wherein u is from 10 to 200 and v is from 10 to
 40. 8. A random polymer formulation according to claim 6, wherein u is from 30 to 170 and v is from 15 to
 30. 9. A random polymer formulation according to claim 6, wherein said random polymer formulation comprises a mixture of copolymers having molecular weights ranging between 2,000 to 90,000 Daltons.
 10. A random polymer formulation according to claim 9, wherein said molecular weights range between 5,000 and 80,000 Daltons.
 11. A random polymer formulation, wherein said random polymer formulation comprises a random terpolymer having the formula:

where: R₁, R₂, R₃ and R₄ are represented by independent radical groups listed below: R₁=C₆H₅, CH₃C₆H₄, (CH₃)₂C₆H₃, (CH₃)₃C₆H₂, (CH₃)₃CC₆H₄; R₂=H, CH₃; R₃=CH₃, C₂H₅, C₄H₉, C₆H₁₃, C₈H₁₇, C₁₀H₂₁, C₁₂H₂₅, C₁₈H₃₇; R₄=H, CN; x=from 2 to 900; Z=from 1 to 300; y=from 1 to
 226. 12. A random polymer formulation according to claim 11, wherein x is from 20 to 850, z is from 10 to 235 and y is from 10 to
 210. 13. A random polymer formulation according to claim 11, wherein x is from 25 to 700, z is from 20 to 220 and y is from 20 to
 200. 14. A set of terpolymers according to claim 5, wherein the molecular weights are in number range from 1,000 to 140,000 Daltons.
 15. A set of terpolymers according to claim 14, wherein the molecular weights are in number range 2,000 to 100,000 Daltons.
 16. A process of reducing the viscosity and depressing the pour point of crude oil, the process comprising: mixing the crude oil with the random polymer of claim 1 in an amount effective to reduce the viscosity and depress the pour point of the crude oil.
 17. A process of claim 16, wherein the crude oil has an API gravity of 9 to 30° API.
 18. A composition comprising crude oil having an API gravity of between 9 and 30° and the random polymer formulation of claim 1, wherein said random polymer formulation is present in an amount sufficient to reduce the viscosity and depress the pour point of the crude oil.
 19. A process of reducing the viscosity and depressing the pour point of crude oil having an API gravity between 9 and 30°, comprising the step of adding at least one random polymer to said crude oil, where said at least one random polymer is selected from the group consisting of

where: R₁, R₂ and R₄ are represented by independent radical groups listed below: R₁ =C₆H₅, CH₃C₆H₄, (CH₃)₂C₆H₃, (CH₃)₃C₆H₂, (CH₃)₃CC₆H₄; R₂ =H, CH3; R₃=CH₃, C₂H₅, C₄H₉, C₆H₁₃, C₈H₁₇, C₁₀H₂₁, C₁₂H₂₅, C₁₈H₃₇; R₄ =H, CN; m=from 10 to 700; n=from 1 to 220 u=from 1 to 220; v=from 1 to 50; x=from 2 to 900; y=from 1 to 226; z=from 1 to 300; wherein said random polymer is present in an amount to reduce the viscosity and depress the pour point of said crude oil.
 20. The process of claim 19, wherein said at least one random polymer is added in an amount of 250 to 4,000 ppm based on the amount of the crude oil.
 21. The process of claim 20, further comprising the step of adding a mixture of the random polymers to the crude oil.
 22. The process of claim 21, wherein said random polymer is a random polystyrene-polyacrylate polymer.
 23. The process of claim 21, wherein said random polymer is a random polyacetate-polyacrylate polymer.
 24. The process of claim 21, wherein said random polymer is a random polystyrene-polyacetate polymer.
 25. The process of claim 21, wherein said random polymer is a random polystyrene-polyacetate-polyacrylate terpolymer.
 26. A random polymer formulation for improving the flow of crude oil having an API gravity between 9 and 30°, which depresses the pour point and/or reduces the viscosity, comprising a random polymer of claim 1 at a concentration ranging from 1 to 60% by weight, and a solvent having a boiling point in the range of 35 to 200° C.
 27. A random polymer formulation according to claim 1, wherein said solvent is a member selected from the group consisting of dichloromethane, chloroform, benzene, toluene, xylenes, jet fuel, naphtha, individually and mixtures thereof.
 28. A random polymer formulation according to claim 11, wherein the random polymer formulation comprises a mixture of random copolymers or terpolymers.
 29. A process of reducing the viscosity and depressing the pour point of crude oil, the process comprising: mixing the crude oil with the random terpolymer of claim 11 in an amount effective to reduce the viscosity and depress the pour point of the crude oil.
 30. The process of claim 29, further comprising the step of adding a mixture of the random terpolymers to the crude oil, in an amount of 250 to 4,000 ppm based on the amount of the crude oil.
 31. A composition comprising crude oil having an API gravity of between 9 and 30° and the random terpolymer formulation of claim 11, wherein said random terpolymer formulation is present in an amount sufficient to reduce the viscosity and depress the pour point of the crude oil. 